Compact Solid Electrolyte Interface Realization Employing Surface-Modified Fillers for Long-Lasting, High-Performance All-Solid-State Li-Metal Batteries.

The implementation of polymer-based Li-metal batteries is hindered by their low coulombic efficiency and poor cycling stability attributed to continuous electrolyte decomposition. Enhancement of the solid electrolyte interface (SEI) stability is key to mitigating electrolyte decomposition. This study proposes surface-functionalized silica mesoball fillers to fabricate a composite polymer electrolyte (MSBM-CPE). As a result of surface modification, the polyethylene oxide matrix benefits from the uniform distribution of the filler, which provides a large surface area and Lewis acid sites. Molecular dynamics simulations reveal that the dissociation energy of lithium bis(trifluoromethanesulfonyl)imide in the filler is fourfold higher (-1.95 eV) than that of the filler-free electrolyte. Consequently, the MSMB-CPE diffusivity is 30 times higher than its filler-free counterpart. The MSMB-CPE of ionic conductivity of 1.16 × 10-2 S cm-1 @60 °C and a venerable Li-ion transference number of 0.81. The excellent compatibility of MSMB-CPE with the Li anode is demonstrated by its stable symmetric cell performance under high current density (200 µA cm-2 @60 °C) for over 5000 h. Approximately 85.60% retention capacity of the [Li/MSMB-CPE/LiFePO4] full cell after 700 cycles. Furthermore, compositional analysis reveals that the SEI layer in MSMB-CPE is smooth with fewer by-products at the electrolyte/Li interface.

SABRE hyperpolarization of nicotinamide derivatives and their molecular dynamics properties.

Signal amplification by reversible exchange hyperpolarization explores the chemical structure and kinetic properties of nicotinamide derivatives. N-Benzyl nicotinamide and nicotinic acid hydrazide compounds display relatively fast dissociation rates of approximately 7-8 s-1 and long proton T1 relaxation times of 5-20 s, respectively. Consequently, these substrates exhibit remarkable signal enhancements, reaching approximately 175 and 102 fold, respectively, underscoring the efficacy of the hyperpolarization technique in elucidating the behavior of these compounds.

Remnant Copper Cation-Assisted Atom Mixing in Multicomponent Nanoparticles.

Nanostructured high-/medium-entropy compounds have emerged as important catalytic materials for energy conversion technologies, but complex thermodynamic relationships involved with the element mixing enthalpy have been a considerable roadblock to the formation of stable single-phase structures. Cation exchange reactions (CERs), in particular with copper sulfide templates, have been extensively investigated for the synthesis of multicomponent heteronanoparticles with unconventional structural features. Because copper cations within the host copper sulfide templates are stoichiometrically released with incoming foreign cations in CERs to maintain the overall charge balance, the complete absence of Cu cations in the nanocrystals after initial CERs would mean that further compositional variation would not be possible by subsequent CERs. Herin, we successfully retained a portion of Cu cations within the silver sulfide (Ag2S) and gold sulfide (Au2S) phases of Janus Cu2-xS-M2S (M = Ag, Au) nanocrystals after the CERs, by partially suppressing the transformation of the anion sublattice that inevitably occurs during the introduction of external cations. Interestingly, the subsequent CERs on Janus Cu1.81S-M2S (M = Ag, Au), by utilizing the remnant Cu cations, allowed the construction of Janus Cu1.81S-AgxAuyS, which preserved the initial heterointerface. The synthetic strategy described in this work to suppress the complete removal of the Cu cation from the template could fabricate the CER-driven heterostructures with greatly diversified compositions, which exhibit unusual optical and catalytic properties.

Proton-Coupled Electron Transfer on Cu2O/Ti3C2Tx MXene for Propane (C3H8) Synthesis from Electrochemical CO2 Reduction.

Electrochemical CO2 reduction reaction (CO2RR) to produce value-added multi-carbon chemicals has been an appealing approach to achieving environmentally friendly carbon neutrality in recent years. Despite extensive research focusing on the use of CO2 to produce high-value chemicals like high-energy-density hydrocarbons, there have been few reports on the production of propane (C3H8), which requires carbon chain elongation and protonation. A rationally designed 0D/2D hybrid Cu2O anchored-Ti3C2Tx MXene catalyst (Cu2O/MXene) is demonstrated with efficient CO2RR activity in an aqueous electrolyte to produce C3H8. As a result, a significantly high Faradaic efficiency (FE) of 3.3% is achieved for the synthesis of C3H8 via the CO2RR with Cu2O/MXene, which is ≈26 times higher than that of Cu/MXene prepared by the same hydrothermal process without NH4OH solution. Based on in-situ attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) and density functional theory (DFT) calculations, it is proposed that the significant electrocatalytic conversion originated from the synergistic behavior of the Cu2O nanoparticles, which bound the *C2 intermediates, and the MXene that bound the *CO coupling to the C3 intermediate. The results disclose that the rationally designed MXene-based hybrid catalyst facilitates multi-carbon coupling as well as protonation, thereby manipulating the CO2RR pathway.

Semiconducting Properties of Delaminated Titanium Nitride Ti4N3Tx MXene with Gate-Tunable Electrical Conductivity.

MXenes have garnered significant attention due to their atomically thin two-dimensional structure with metallic electronic properties. However, it has not yet been fully achieved to discover semiconducting MXenes to implement them into gate-tunable electronics such as field-effect transistors and phototransistors. Here, a semiconducting Ti4N3Tx MXene synthesized by using a modified oxygen-assisted molten salt etching method under ambient conditions, is reported. The oxygen-rich synthesis environment significantly enhances the etching reaction rate and selectivity of Al from a Ti4AlN3 MAX phase, resulting in well-delaminated and highly crystalline Ti4N3Tx MXene with minimal defects and high content of F and O, which led to its improved hydrophobicity and thermal stability. Notably, the synthesized Ti4N3Tx MXene exhibited p-type semiconducting characteristics, including gate-tunable electrical conductivity, with a current on-off ratio of 5 × 103 and a hole mobility of ∼0.008 cm2 V-1 s-1 at 243 K. The semiconducting property crucial for thin-film transistor applications is evidently associated with the surface terminations and the partial substitution of oxygen in the nitrogen lattice, as corroborated by density functional theory (DFT) calculations. Furthermore, the synthesized Ti4N3Tx exhibits strong light absorption characteristics and photocurrent generation. These findings highlight the delaminated Ti4N3Tx as an emerging two-dimensional semiconducting material for potential electronic and optoelectronic applications.